Method and compositions for the dyeing of human hair

ABSTRACT

In an aqueous composition for dyeing human hair comprising an oxidation dyestuffs combination of a developer component and a coupling component and customary oxidation dyestuff adjuvants, the improvement which comprises utilizing as said oxidation dyestuff combination, (a) from 0.3 to 5 percent by weight of said composition, of a coupling component 3-aminopyrazol-5-one having the formula WHEREIN R is selected from the group consisting of -NH-CO-R1, NH-CO-NH-R1 and -NH-CS-NH-R1 wherein R1 is selected from the group consisting of a hydrocarbon radical with 1 to 12 carbon atoms and a heterocyclic radical, and (b) from 0.3 to 5 percent by weight of said composition, of a developer component compound, known for hair dyes, selected from the group consisting of aromatic polyfunctional amines having at least one primary amino group and at least one polyfunctional group in the ortho or para position and heteroaromatic amino compounds as well as the method of dyeing human hair utilizing said oxidation dyestuff combination of a developer component and a coupling component.

United States Patent [191 Wiskott METHOD AND COMPOSITIONS FOR THE DYElNG OF HUMAN HAIR [75] Inventor: Erik Wiskott, Bottmingen Basel-Land, Switzerland [73] Assignee: Therachemie Chemisch Therapeutische Gmbl-l, Dusseldorf, Germany [22] Filed: Sept. 24, 1970 [21] App]. No.2

[30] Foreign Application Priority Data Oct. 2, 1969 Germany 1949748 [52] US. Cl. 8/102, 8/11 [51] Int. Cl A6lk 7/12 [58] Field of Search 260/310 A; 96/565; 8/102, 11

[56] References Cited UNITED STATES PATENTS 2,311,082 2/1943 Porter et al 260/310 A X 2,369,489 2/1945 Porter et al 96/565 3,325,482 6/1967 Monbaliu et al 260/310 A X 3,617,167 ll/l97l Berth et al. 8/l0.2 3,674,414 7/l972 Kalopissis et al. 8/ll 3,993,071 7/l967 Monbaliu et al 96/565 Primary Examiner-Stanley J. Friedman Attorney, Agent, or Firm-Hammond and Littell [57] ABSTRACT In an aqueous composition for dyeing human hair comprising an oxidation dyestuffs combination of a Nov, l9, i974 developer component and a coupling component and customary oxidation dyestuff adjuvants, the improvement which comprises utilizing as said oxidation dyestuff combination, (a) from 0.3 to .5 percent by weight of said composition, of a coupling component 3- aminopyrazol-S-one having the formula Ill 1 0 wherein R is selected from the group consisting of NH--COR ---Nl-l CO--Nl-l-R and N- H-CS-NH-R wherein R is selected from the group consisting of a hydrocarbon radical with l to 12 carbon atoms and a heterocyclic radical, and (b) from 0.3 to 5 percent by weight of said composition, of a developer component compound, known for hair dyes, selected from the group consisting of aromatic polyfunctional amines having at least one primary amino group and at least one polyfunctional group in the ortho or para position and heteroaromatic amino compounds as well as the method of dyeing human hair utilizing said oxidation dyestuff combination of a developer component and a coupling component.

5 Claims, N0 Drawings THE PRIOR ART The use of oxidation dyestuffs for dyeing human hair has been known for many years. The so-called developer components and coupling components are used for the production of the oxidation dyestuffs. It has already been suggested to use 3-amino-pyrazolones as coupling components and aromatic polyfunctional amines or 4-amino pyrazolones as developer components. Good dyeing results can be achieved in many cases with these dyestuff combinations, which are transformed into dyes on the hair by oxidation either with air or particularly by the addition of chemical oxidants, like hydrogen peroxide. It was found, however, that the colors, particularly thev yellow and brown shades, cannot be readily obtained by these oxidation dyestuff combinations.

OBJECTS OF THE INVENTION An object of the present invention is, in an aqueous composition for dyeing human hair comprising an oxidation dyestuffs combination of a developer component and a coupling component and customary oxidation dyestuff adjuvants, the improvement which comprises utilizing as said oxidation dyestuff combination, (a) from 0.3 percent to 5 percent by weight of said composition, of a coupling component 3-aminopyrazol-S-one having the formula wherein R is selected from the group consisting of N- H-COR NH-CONHR and NHC- S--NH-R wherein R is selected from the group consisting of alkyl having one to six carbon atoms, phenyl, halophenyl, alkylphenyl having 7 to 12 carbon atoms, alkoxyphenyl having 7 to 12 carbon atoms, dialkylaminophenyl having one to four carbon atoms in the alkyls, cyclohexyl, alkylcyclohexyl having 7 to 12 carbon atoms, pyridyl and piperidyl, and (b) from 0.3 percent to 5 percent by weight of said composition, of a developer component compound selected from the group consisting of I) aromatic amines having the formulae wherein R is selected from the group consisting of OH, NH NHR and NR R is selected from the group consisting of alkyl having one to four carbon atoms, hydroxyalkyl having one to four carbon atoms, phenyl and p-aminophenyl, and R is selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms, hydroxyl and amino, (2) 4-amino-pyrazolones having the formula wherein R is selected from the group consisting of hydrogen, alkyl having, I to [0 carbon atoms, phenyl. paminophenyl, p-halophenyl, p-hydroxyphcnyl. p methylaminophenyl, p-dimethylaminophenyl, carboxyl, carbo-lower alkoxy, carbamoyl, CONHR and CONR' R having the above assigned values, and R is selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, phenyl, alkylphenyl having 7 to 10 carbon atoms, alkoxyphenyl having 1 to 10 carbon atoms, aminophenyl-hydroxyphenyl, carboxyphenylfcarbamoylphnyl, "suirafili'riy'r'ana" timinosuifonylphenyl, and (3) amino-pyridines having the formula wherein R is selected from the group consisting of hydrogen, alkyl having one to four carbon atoms and phenyl.

Another object of the present invention is in the process of dyeing human hair which comprises treating the hair at temperatures of from 10C to 40C with an aqueous composition for dyeing human hair comprising an oxidation deystuff combination of a developer component and a coupling component and customary dyestuff adjuvants, in the presence of an oxidizing agent, the improvement which comprises utilizing as said oxidation dyestuff combination, (a) from 0.3 percent to 5 percent by weight of said composition, of a coupling component 3-amino-pyrazol-5-one having the formula wherein R is selected from the group consisting of -N- HCOR NHCO--NHR, and -NH-C- SNH-R wherein R is selected from the group consisting of alkyl having one to six carbon atoms, phenyl, halophenyl, alkylphenyl having 7 to 12 carbon atoms, alkoxyphenyl having 7 to l2 carbon atoms, dialkylaminophenyl having one to four carbon atoms in the alkyls, cyclohexyl, alkylcyclohexyl having 7 to 12 carbon atoms, pyridyl and piperidyl, and (b) from 0.3 percent to 5 percent by weight of said composition, of a developer component compound selected from the group consisting of l) aromatic amines having the formulae wherein R is selected from the group consisting of H,

NH NHR' and NR' R is selected from the group consisting of alkyl having one to four carbon atoms, hydroxyalkyl having one to four carbon atoms, phenyl and p-aminophenyl, and R is selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms, hydroxyl and amino, (2) 4-amino-pyrazolones having the formula N(Ra)2 wherein R is selected frorn the group consisting of hydrogen, alkyl having one to four carbon atoms and phenyl.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The new method of dyeing human hair with solutions, emulsions or creams, which contain oxidation dyestuffs and other additives customary for hair dyes, is characterized in that the hair is treated in the presence of an oxidizing agent and at temperatures from l0C to 40C with 3-aminopyrazol-5-ones (coupling components) of the general formula I wherein R represents --NHCO-R or -N- HCONH-R or -NH*-CSNH-R and R denotes a hydrocarbon radical with l to l2 carbon atoms or a heterocyclic radical, and of developer components, known for hair dyes, based on aromatic dior polyfunctional amines with at least one primary amino group as well as one additional functional group in para-position, or on heteroaromatic amino compounds.

The hydrocarbon radical R, can be present in the form of an aliphatic, aromatic or cyclo-aliphatic radical and also contain halogen atoms, particularly chlorine, or, in the case of cyclic compounds, alkylor alkoxy groups or dialkylamino groups with alkyl chains of one to four carbon atoms. Suitable heterocyclic radicals for R are the pyridyl and piperidyl radicals.

In a preferred embodiment R, can be alkyl having one to six carbon atoms such as methyl, ethyl, isopropyl, n-propyl, n-butyl; phenyl; halophenyl such as pchlorophenyl; alkylphenyl having from 7 to 12 carbon atoms such as p-methylphenyl, p-ethylphenyl, opropylphenyl; alkoxyphenyl having from 7 to 12 carbon atoms such as o-methoxyphenyl, pisopropoxyphenyl; dialkylaminophenyl having one to four carbon atoms in the alkyl such as pdimethylaminophenyl; cyclohexyl; alkylcyclohexyl having from 7 to l2 carbon atoms such as methylcyclohexyl; pyridyl; and piperidyl.

Preferably 3-aminopyrazol-5-ones of the general formula ll are used as the coupling component compound where R is alkyl having one to six carbon atoms.

As examples of readily available substituted 3-aminopyrazol-5-ones the following are mentioned: l-phenyl-3-acetamido-pyrazol-5-one 1-phenyl-3-benzamido-pyrazol-S-one l-phenyl-3-( 3 '-cyclohexylureido )-pyrazol-5-one l-phenyl-3-(3-phenylureido)-pyrazol-5-one l-phenyl-3-(3'-p-chlorophenylureido)-pyrazol-5-one l-phenyl-3-(3'-ethyl-2-thioureido)-pyrazol-5-one Suitable developer components are aromatic di-and polyfunctional amines with at least one primary amino groups as well as one additional functional group in the ortho or para, preferably the para position. Preferably these compounds are ortho or para aromatic diamines or hydroxyamines which can contain in addition other functional groups, such as -OH, NH NHR and -N(R') The preferred aromatic developer components of the aromatic amine type are aromatic amines having the formulae R3 R2 R --Nm and Q-Nm wherein R, and R are each, in general, hydrogen or an organic radical with l to 10 carbon atoms.

The organic radical R of the 4-amino-pyrazolone can consist, for example, of an alkyl radical with l to l carbon atoms or of an aryl or heterocyclic radical. Furthermore, functional groups such as --OH, NH NHCH N(CH or halogen atoms, particularly chlorine, can be present. Furthermore, suitable organic radicals are the following groups: COOH, COOR', CONHR' and CON(R') where R is lower alkyl or hydroxyalkyl with one to four carbon atoms.

The organic radical R of the 4-amino-pyrazolone may be an alkyl radical of l to carbon atoms or also an aryl or heterocyclic radical. E inctional groups may Preferably in the above formula Ill, R is selected from the group consisting of hydrogen, alkyl having I to l0 carbon atoms, phenyl, p-aminophenyl, phalophenyl, p-hydroxyphenyl, p-methylaminophenyl,

5 p-dimethylaminophenyl, carboxyl, carbo-lower alkoxy, CONHR' and CONR R. having the above assigned values, and R is selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, phenyl, alkylphenyl having 7 to 10 carbon atoms, al koxyphenyl having 1 to 10 carbon atoms, aminophenyl, hydroxyphenyl, carboxyphenyl, carbamoylphenyl, sulfophenyl and aminosulfonylphenyl. Particularly suitable is lphenyl-3-carbamoyl-4-aminopyrazol-5onc.

It is frequently of advantage to use the 4- aminopyrazol-S-ones in the form of their salts with inorganic or organic acids, particularly hydrochloric or sulfuric acid, which reduces their sensitivity to air.

Suitable aminopyrdines which can be utilized as developer component compounds are the aminopyridines having the formula wherein R is selected from the group consisting of hyfurther also be present. In particular, hydrocarbon radicals with l to ID carbon atoms can be present which contain as functional groups OH, -NH COOH, -CONH SO H and'SO NH As an aromatic radical, in particular, phenyl is utilized for R The latter can contain alkylor hydroxyalkyl groups with one to four carbon atoms or other substituents, such as NH --OH, -COOH, CONH Ol' "SO gNHg.

YELLOW BROWN DYESTU FF As with other oxidation dyestuffs, the colors can be developed both by atmospheric oxygen and by chemical oxidants. Preferably hydrogen peroxide or its addition products, like percarbamide, melamine perhydrate and sodium perborate are used. The dyeing of the hair is effected at temperatures of to 40C, preferably at room temperature. The dye treatment of the living human hair is preferably for a period of 10 minutes to 1 hour followed by a rinsing of the hair.

The hair dyeing compositions may be applied in the form of aqueous solutions, but expecially in the form of creams or emulsions. For this purpose, the developer and coupling component compounds are mixed with any optional wetting agents or washing compositions, especially anionic or non-ionic substances. Suitable wetting and washing agents are especially alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid ethanolamides, products of addition of ethylene oxide to higher alkyl amines and fatty alcohols, and fatty alcohol alkyl ether and polyalkyl ether sulfates.

The absorptive capacity of the above-mentioned dyestuffs is also good when they are in admixture with such compositions. Consequently, the hair dyes can be produced in the form of shampoos, especially of cream shampoos, which are much desired in practice.

Further, thickeners such as, for example, methylcellulose, starch, higher fatty alcohols, vaselines, paraffin oil and fatty acids, and also perfume or hair conditioning substances such as, for example, pantothenic acid and cholesterol, may be admixed with the compositions of the invention.

The added substances are used in the amount customary for these purposes. Suitable added amounts of wetting agents are, especially, 0.5 percent to 30 per cent by weight, and of thickeners, are 0.1 percent to 25 percent by weight, referred in each case to the total composition. The concentration of the dyestuff components (developer and coupling components) is to a certain extent dependent on the purpose of use and amounts, in each case, to 0.3 to 5 percent by weight, preferably 0.5 to 2.5 percent by weight. These quantities are also with reference to the total composition.

The hair dyes are adjusted so that they are alkaline, preferably to a pH value of 8 to 10. The dyeings obtained with the hair dyes described above have good properties with respect to light, washing and rubbing.

\ EXAMPLE 1 Parts by weight of l-phenyl-3carbamoyl-4- aminopyrazol-S-one. H 80, and 1.8 parts by weight of l-phenyl-3-(3'-mcthylureido)pyrazol-5-one were dissolved in water containing ammonia and 5 parts by weight of ethanol. 50 Parts by weight of an emulsion formed from 10 parts by weight of a fatty alcohol (hy- 5 drocarbon chain length C C 26 parts by weight of sodium lauryl ether sulfate and 64 parts by weight of water were added thereto. The pH was adjusted to 9.5, l part by weight of hydrogen peroxide was added and the dye composition was made up to parts by 10 weight with water.

The dye cream so obtained dyed grey hair a yellowbrown when treated at room temperature over a period of 30 minutes. After the dye treatment, the hair was rinsed with water and shampooed.

EXAMPLE 2 2 Parts by weight of p-(2,5-diaminopyridine)- dihydrochloride and 2 parts by weight of l-phenyl-3- (3'-ethylureido)-pyrazol-5-one were dissolved in water and worked into an emulsion as in Example 1. The mixture was adjusted to a pH of 9.5. 1 Part by weight of hydrogen peroxide was added and made up to 100 parts by weight with water.

The dye cream so obtained dyed grey hair a yellow brown when treated at room temperature over a period of 30 minutes. in place of hydrogen peroxide, equivalent amounts of melamine perhydrate, urea perhydrate or sodium perborate may be employed with comparable results.

EXAMPLE 3 used as developer and coupling components. Under similar conditions with a period of action of 25 minutes at a temperature of about 30C, the dye colors indicated in the right column of the Table were obtained. The coupling components used correspond all to the general formula 1.

Kaila? For the salte of simplicity, Table lorfly the group R.

Compound No. R Developer component Dye color 1 l-pheny1-3-earbamoyl-4'amino- Yellow brown.

CH3 g NH pyrazol-fi-one.

2 .do Brown.

CqH5-( /'NH 3 (H) d0 Light brown.

CiHr-NHC-NH 4 El) .do Yellow brown.

CzHsNHCNH- 5 S do Pale brown.

Compound No. R Developer component Dye color 6; O l-phenyl ri1ini$- Ye il bw brown.

1 G3IIT I THI (||J NH pyrazoI-S-one.

7 n do Brown.

n-O H NHK INH 8 0 do Grey brown.

01NH%-NH 9 do Brown.

C2H5NH( JNH 10 v 2 0 ...do Yellow brown.

H NH-( gNH- 11 .A 0 do Red brown.

n-CaHr-NH( JNH 12 2 do Grey brown.

nC4Hq-NH( NH 13 0 p-Toluy1enediamine Dark red brown.

i4 I. 0 do Do.

CIIa--NH- 15 2. 0 -.do D0.

-NH-(JNH 16 0 do D0.

C2H5-NH-(HJNH 17 S do Red brown.

@mn--NH- 18 do Dark red brown.

CHa-NH-( ,NH

19 0 .do D0.

I1-C4Hn-NH-g -NH- 20 0 d0 Brown.

Cl@NH-(JNH 21 S do Dark brown.

C2H5-NH( 3NH 22 v, do Red, brown.

H NH NH- 23 .A 0 do Dark red brown.

n-CsH1NH-( JNH- 24 S de Brown.

n-C4H NH-ylNH 25 0 p-Diaminoanlsole Dark brown.

26 2 do Violet brown.

CHr-NH- 0 .do Brown. @NH-(J-NH- 28 0 ....do Red brown.

C;H5NH J-NH 29 0 .d0 Do.

TABLE I- Continued Compound. No.

Dye color Developer component rain.

..do Dark red.

. do Dark brown red.

p-Aminodiphenylamine. Violet grey.

2,5-diamlnopyrldine..-.....

human h a irfthe hydrogen peroxide pl es, other ratios such as 0.8 to 1.2 to 1 may be emshould preferably be added to the dye cream just prior ployed with comparable results.

When dyeing to its application to the hair. While substantially equi- 65 The preceding specific embodiments are illustrative molar amounts of the developer component and the of the practice of the invention. It is to be understood, coupling component have been utilized in the examhowever, that other expedients known to those skilled 13 in the art may be employed without departing from t he spirit of the invention or the scope of the appended claims.

I claim: 1. in the process of dyeing human hair which comprises applying to the hair at temperatures of from to 40C an effective amount of an aqueous composition for dyeing human hair comprising an oxidation dyestuff combination of a developer component and a coupling component at a pH from 8 to 10 in the presence of an oxidizing agent, the improvement which comprises utilizing as said oxidation dyestuff combination, (a) from 0.3 to 5 percent by weight of said composition, of a coupling component S-amino-pyrazol-S-one having the formula wherein R is selected from the group consisting of alkyl having one to six carbon atoms, phenyl, halophenyl, and cyclohexyl, and (b) from 0.3 to 5 percent by weight of said composition, of a developer component compound selected from the group consisting of (1) an aromatic amine, (2) a 4-amino-pyrazolone, and (3) an amino-pyridinet 2. The process of claim 1 wherein said developer component and said coupling component are present in substantially equimolar amounts.

3. The process of claim 1 wherein said developer component compound is selected from the group consisting of l-phenyl-3-carbamoyl-4-amino-pyrazol- 5-one, p-toluylene-diamine, p-diaminoanisole, p-(N,N- dimethylamino)-aniline, p-aminodiphenylamine and 2,5-diaminopyridine.

4. The process of claim 1 wherein said developer component is said 4-amino-pyrazolone.

5. The process of claim 4 wherein said 4-aminopyrazolone is l-phenyl-3-earbamoyl-4-amino-pyrazol- 5-on e. 

1. IN THE PROCESS OF DYEING HUMAN HAIR WHICH COMPRISES APPLYING TO THE HAIR AT TEMPERATURES OF FROM 10* TO 40*C AN EFFECTIVE AMOUNT OF AN AQUEOUS COMPOSITION FOR DYEING HUMAN HAIR COMPRISING AN OXIDATION DYESTUFF COMBINATION OF A DEVELOPER COMPONENT AND A COUPLING COMPONENT AT A PH FROM 8 TO 10 IN THE PRESENCE OF AN OXIDIZING AGENT, THE IMPROVEMENT WHICH COMPRISES UTILIZING AS SAID OXIDATION DYESTUFF COMBINATION, (A) FROM 0.3 TO 5 PERCENT BY WEIGHT OF SAID COMPOSITON, OF A COUPLING COMPONENT 3-AMINO-PYRAZOL-5-ONE HAVING THE FORMULA 1-PHENYL,3-(R1-CO-NH-),5-(O=)PYRAZOLIDINE WHEREIN R1 IS SELECTED FROM THE GROUP CONSISTING OF ALKYL HAVING ONE TO SIX CARBON ATOMS, PHENYL HALOPHENYL, AND CYCLOHEXYL, AND (B) FROM 0.3 TO 5 PERCENT BY WEIGHT OF SAID COMPOSITION, OF A DEVELOPER COMPONENT COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) AN AROMATIC AMINE, (2) A 4-AMINO-PYRAZOLONE, AND (3) AN AMINO-PYRIDINE.
 2. The process of claim 1 wherein said developer component and said coupling component are present in substantially equimolar amounts.
 3. The process of claim 1 wherein said developer component compound is selected from the group consisting of 1-phenyl-3-carbamoyl-4-amino-pyrazol-5-one, p-toluylene-diamine, p-diaminoanisole, p-(N,N-dimethylamino)-aniline, p-aminodiphenylamine and 2,5-diaminopyridine.
 4. The process of claim 1 wherein said developer component is said 4-amino-pyrazolone.
 5. The process of claim 4 wherein said 4-amino-pyrazolone is 1-phenyl-3-carbamoyl-4-amino-pyrazol-5-one. 